Analytical Chemistry Division
2016
Analytical Chemistry
• Not JUST titrations!
• We’re doing research in topics as diverse as better batteries, labs‐on‐chips, forensics, explosives detection and degradation, and better body armor.
• We use almost every instrument you’ve seen plus some.
• Two of the departments’ scanning probe instruments are in the Analytical Division.
Analytical Chemistry Members
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CAPT Rob Calhoun
Professor Graham Cheek
Professor Christine Copper
Professor Judith Hartman
Professor Dianne Luning Prak
Professor Dan O’Sullivan
Professor Maria Schroeder
Associate Professor Ron Siefert
Professor Paul Trulove
CAPT Rob Calhoun, USN, Ph.D.
Mi‐237, 3‐6635
calhoun@usna.edu
Electroanalytical Chemistry
Electroanalytical chemistry
• Current major project:
– Development of a rapid screening technique for new anti‐corrosion coatings for Naval Aviation using scanning electrochemical microscopy (SECM).
– Work will move into screening of additive materials (AM) since they are showing differences from the same alloys when forged.
Experimental Visualization
SECM Tip
0.1V
FcMeOH
Solution
5‐20 µm
Substrate
0.5V to 3.0V
Soluble oxide? Ferrocene
?
Fc+
Coating
Fc
Aluminum Substrate
TABLE I
Tip current (nA) at
indicated substrate
potential vs. Ag/AgCl
Sample
non-chromated primer on
anodized Al
waterborne primer on alodine
pretreated Al
chromated primer on alodine
pretreated Al
1.0V 1.5V 1.8V 2.5V
0.28
0.28 3.50 10.00
0.25 0.25 1.60
0.28 0.18 0.18
‘Screening of Novel Anti‐Corrosion Coatings by Scanning Electrochemical Microscopy’, Lee, C., Dorriety, W., Hanrhan, R., Calhoun, R., ECS Transactions, 2015 66(30): 65‐71
RESEARCH INTERESTS
Prof. Graham Cheek
Mi 144 36625
Electrochemistry of organic compounds
1. Bio‐electrochemistry of amino acids
2. Effect of Lewis acids on reaction pathways
cysteine
tryptophan
3. Electrochemical fluorination
F2
2 F‐ → F2 + 2 e‐
+ RH → RF + HF
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Solvents : Water, ionic liquids, adiponitrile
Forensic Applications
1. Soil Characterization : X‐Ray Fluorescence
2. Paper / Ink Characterization : Raman Spectroscopy CF3 SO3 -
RESEARCH INTERESTS Prof. Graham Cheek
Bio‐electrochemistry of amino acids
Solvents
pH 7 aqueous buffer
Nonaqueous solvents
Ionic liquids
Effect of metal ions ( Zn2+ ) on electrochemical behavior
Use of NMR, UV‐VIS ?
Prof. Dianne Luning Prak (prak@usna.edu) & Prof. Paul Trulove
January 20, 2016: Navy launched Carrier Strike Group out of San Diego powered by mixtures of petroleum‐based and bio‐based fuel. http://greenfleet.dodlive.mil/energy/great‐green‐fleet/
Midn 1/C Bridget Lee
Fuel certification program/Office of Naval Research Goal: How does chemical structure impact the physical and chemical properties of fuels? density, viscosity, surface tension, speed of sound, bulk modulus, flash point, enthalpy of combustion, distillation behavior, combustion in diesel engines
Luning Prak, D. J., Jones, M. H., Trulove, P. C., McDaniel, A. M., Dickerson, T., Cowart, J., 2015, “Physical and Chemical Analysis of Alcohol‐to‐Jet (ATJ) Fuel and Development of Surrogate Fuel Mixtures,” Energy and Fuels, 29, 3760 − 3769.
Photolysis of munitions constituents and algal toxins
Unexploded Ordnance
in shallow waters
How can the photolysis behavior of munitions constituents and algal toxins in be sped up by the addition of photosensitizers:
∙ riboflavin
∙ dissolved organic matter?
http://www.SERDP.org
Midn 1/C Evelyn Rios
SUNSHINE LAB
Solar Simulator
HPLC with autosampler
Project involves
∙ preparing solutions ∙ using solar simulator
∙ analyzing samples with HPLC
∙ identifying products solid‐phase extraction, LC/MS
Luning Prak, D.J., Breuer, J.E.T., Rios, E.A., Jedlicka, E.E., O’Sullivan, D.W., “Influence of pH, Temperature, Salinity, and Dissolved Organic Matter on the Photolysis of 2,4,6‐trinitrotoluene in Seawater and Estuary Water,” submitted to Marine Chemistry, Dec. 2015.
Oxidation of formaldehyde in atmospheric aerosols
Professor O’Sullivan:
Atmospheric aerosols:
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Life time 4 to 7 days
Size 0.01 to 10 m
Large surface area
Experience a number of hydration and dehydration cycles.
Examine the oxidation kinetics of formaldehyde as a source of formic acid:
• In aqueous solutions with compositions similar to aerosols
• H2CO oxidation is thought to be dominated by gas phase chemistry
• Examine aqueous oxidation as a function of pH, ionic composition, and various oxidants
• O3, H2O2 and metal catalysis
Figure from the Leibniz‐Institute for Tropospheric Chemistry
Professor Schroeder’s Research Interests
Harold Edgerton, photographer
Projectile hitting elastomer at > 500 mph
‐ Improved Polymer Coatings for:
‐ Military Transport (Humvees)
‐ Body Armor
‐ Hazardous Material Transport
‐ Transparent Armor
‐ Education Research/Laboratory Development
‐ Understanding Plebe learning
‐ Experiments in support of Chemistry of Cooking course or IL
Motivation for Coatings Research
• To understand the mechanisms  Polymer synthesis, characterization, of impact protection of processing
polymer‐coated surfaces
projectiles hitting  Engineering, physical and elastomers at high speed
mechanical testing
protection no protection
 Materials Science
• To understand temp effects (Tg)  Ballistic testing
• To improve armor protection
 Basic research with military Current Research Student
applications
John Chamberlain, ’15
Research Collaboration:
Naval Research Laboratory (NRL) Another Research Area
Understanding How Plebes Learn
• Educational Research Study
• Selected topics (spectroscopy, laboratory concepts)
• What helps plebes learn and retain complex chemistry topics?
• Can the lab be used better to teach concepts? (MORE labs)
• How can we develop better “transfer” in students?
• Can “molecular‐level” thinking help reinforce concepts?
Midn 1/C Stephanie Moore
Demo Midn Moore developed – hope to publish it
Ron Siefert
Associate Professor
3‐6336 (office), Mi‐243 (office), Mi‐240 (lab)
Current Project / Development of Nanoporous Sorbent Materials for “Lab on a Chip”
Novel Sorbents (PMOs: periodic mesoporous organisilicas) ‐For Analysis of Nitroenergetics (i.e, explosives)
‐For Analysis of Perchlorates (used as propellants)
‐As a substrate for catalysts to destroy contaminants
Past
Projects
Vehicle NH3 Emissions
Agricultural NH3 Emissions
Ammonia & Nitrate Measurements in the Chesapeake Bay Iron in Marine Aerosols
Deposition of Nutrients to Surface Waters
Enhanced Detection of Explosives and Related Compounds
Nanoporous Photocatalysts for Decontamination of Nerve Agents
Lab on a Chip
Microfluidic devices using electro‐osmotic flow.
OBJECTIVE: Develop organosilicas as sorbents applicable to the preconcentration of nitroenergetics
and perchlorates for enhancement of in situ detection techniques
APPROACH: Characterize the binding characteristics (e.g., selectivity, capacity, kinetics) of imprinted PMOs for nitroenergetics and perchlorate propellants. Use of HPLC and IC.
N
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R
NEW INSIGHTS
QUANTITATIVE IMPACT
Natural polymers are renewable
materials that have many attractive
properties. Some natural silks have
strength and toughness comparable
to the best synthetic polymers.
The ability to modify and tailor the
shape and properties of natural
polymers is limited.
N
R''
R'
CH3COO−
Ionic Liquids Solvents
We have shown that ionic liquids
are powerful solvents for the
dissolution and processing of a
wide variety of natural polymers.
The solvating ability of ionic
liquids provides a powerful tool for
the modification and processing of
natural polymers.
Department of Chemistry
MAIN ACHIEVEMENTS
Investigated the ionic properties of fiber welding
solvents and the impacts of biopolymer on them
Studied the optimization of Inkjet printing of
biopolymers from ionic liquid solvents
Prepared nanoscale bimetallic catalysts in natural
polymer materials and used them to fabricate a
catalytic membrane via natural fiber welding
Developed natural fiber welded antimicrobial
biopolymer and metal oxide coatings on cellulose
substrates
Demonstrated a continuous fiber welding process
that significantly improves the mechanical
properties of treated yarns
END-OF-PHASE GOAL
STATUS QUO
Natural Polymers
Producing natural materials
with dramatically enhanced
mechanical properties
Enabling tuneable natural
material properties with high
spatial resolution
Facilitating the integration of
functional solid materials with
electrical, magnetic and optical
properties into natural fiber
matrices
Develop multi-functional natural
materials and coatings with
unique electronic, optical, and
sensing properties for Air Force
and DoD relevant applications
in areas such as ballistic
protection, energy storage,
microelectronics, stealth, laser
eye protection, optical
computing, chem./bio sensing,
in-situ medical applications
Biopolymer Properties
Fiber
Dragline Spider Silk
(Nephila clavipes)
Silkworm Cocoon
Silk (Bombyx mori)
Nylon 66
Cotton
Kevlar 49
Steel
Elongation
at Failure
(%)
10-40
Modulus
(GPa)
Strength
(GPa)
Density
(g/cm3)
Energy to
Break (J/g)
1-30
0.3-1.8
1.35
30-125
15-35
5
0.6
1.45
70
18
6-7
2.5
8
5
6-11
124
200
0.88
0.3-0.7
2.8
2
1.14
1.50
1.44
13.0
80
5-15
15
2
D.L. Kaplan, S.J. Lombardi, W. Muller, S. Fossey, in Biomaterials: Novel Materials from Biological Sources (Ed: Byrom D.), Stockton Press, New York 1991.
Department of Chemistry
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Inkjet Printing with Ionic Liquid “Inks”
Dimatix Materials Printer
Movie Obtained from Wikipedia http://en.wikipedia.org/wiki/Micro_Piezo
MIDN Audrey Head
500 µm
3
m
m
3 mm
500 µm
Department of Chemistry
Printing
Ionic Liquid @ 70 °C
Ionic Liquid Printed on Cotton Paper
Integration of Chitin and Chitosan into
Cellulose Surfaces
• Chitin  most abundant biopolymer after cellulose
− Similar in structure to cellulose
− Can be harvested from waste materials (i.e. shrimp shells)
− Chitosan generated from Chitin by deacetytalation
MIDN Molly Chandler*
• Chitin and Chitosan have desirable properties
− Antimicrobial
− Metal complexation/absortion
*Lt. Robert Russell – Lead Research Advisor
MIDN Robert Nolan*
21
Department of Chemistry
GFP E. coli Testing of NFW Chitin on
Cotton Cloth
408 nm
488 nm
No Welding
No Welding
• Con-Focal Fluorescence (CFM)
Images of Untreated and NFW
Chitin on Aida Cotton Cloth
• Modified Version of *ASTM
(E2722-09)
500 μm
IL & 0.5% chitin
500 μm
IL & 0.5% chitin
‒ Standard test method for the
screening assessment of
antimicrobial activity in fabric and
air filter media
• Welding done for 120 min at R.T.
Samples coated with 4×105
cells/mL GFP E. Coli w/ agar, 72
hrs growth.
500 μm
Department of Chemistry
500 μm
Use of Ionic Liquids to Fabricate
Biopolymer Composite Materials
Knitted Electrochemical Capacitors for Smart Textiles*
Bamboo (0.54 mg/cm)
MIDN Katie Ryall
23
Department of Chemistry
*Collaboration with Drexel University
Knitted Linen/Bamboo/Viscose Capacitors!
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Yarn
Electrode
Yarn
Separator
Yarn
Electrode
Department of Chemistry
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Department of Chemistry
Questions?